CN100404223C - Process for production of hydrogel particles and process for cutting of high-concentration hydrogel sheet - Google Patents

Process for production of hydrogel particles and process for cutting of high-concentration hydrogel sheet Download PDF

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Publication number
CN100404223C
CN100404223C CNB2004100749806A CN200410074980A CN100404223C CN 100404223 C CN100404223 C CN 100404223C CN B2004100749806 A CNB2004100749806 A CN B2004100749806A CN 200410074980 A CN200410074980 A CN 200410074980A CN 100404223 C CN100404223 C CN 100404223C
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serialgram
cutting
water
absorbing resin
hydrogel
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CN1590057A (en
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笹部昌纯
野木幸三
阪本繁
藤田康弘
森田晃弘
服部浩明
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D7/00—Details of apparatus for cutting, cutting-out, stamping-out, punching, perforating, or severing by means other than cutting
    • B26D7/08—Means for treating work or cutting member to facilitate cutting
    • B26D7/088—Means for treating work or cutting member to facilitate cutting by cleaning or lubricating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/0006—Cutting members therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/01—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work
    • B26D1/12—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis
    • B26D1/14—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter
    • B26D1/22—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter coacting with a movable member, e.g. a roller
    • B26D1/225—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter coacting with a movable member, e.g. a roller for thin material, e.g. for sheets, strips or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/01—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work
    • B26D1/12—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis
    • B26D1/14—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter
    • B26D1/24—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter coacting with another disc cutter
    • B26D1/245—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a circular cutting member, e.g. disc cutter coacting with another disc cutter for thin material, e.g. for sheets, strips or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/01—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work
    • B26D1/12—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis
    • B26D1/25—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a non-circular cutting member
    • B26D1/34—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a non-circular cutting member moving about an axis parallel to the line of cut
    • B26D1/38—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a non-circular cutting member moving about an axis parallel to the line of cut and coacting with a fixed blade or other fixed member
    • B26D1/385—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which does not travel with the work having a cutting member moving about an axis with a non-circular cutting member moving about an axis parallel to the line of cut and coacting with a fixed blade or other fixed member for thin material, e.g. for sheets, strips or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/56—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which travels with the work otherwise than in the direction of the cut, i.e. flying cutter
    • B26D1/62—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which travels with the work otherwise than in the direction of the cut, i.e. flying cutter and is rotating about an axis parallel to the line of cut, e.g. mounted on a rotary cylinder
    • B26D1/626—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor involving a cutting member which travels with the work otherwise than in the direction of the cut, i.e. flying cutter and is rotating about an axis parallel to the line of cut, e.g. mounted on a rotary cylinder for thin material, e.g. for sheets, strips or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D9/00—Cutting apparatus combined with punching or perforating apparatus or with dissimilar cutting apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/04—Making granules by dividing preformed material in the form of plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/0006—Cutting members therefor
    • B26D2001/002—Materials or surface treatments therefor, e.g. composite materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0058—Liquid or visquous
    • B29K2105/0061—Gel or sol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0092—Other properties hydrophilic

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Forests & Forestry (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

An object of the present invention is to make it possible that: a high-concentration hydrogel sheet, which is suitable for production of high-performance water-absorbent resin particles, is cut efficiently without involving the adhesion to such as cutting-blades; and the subsequent disintegration operation is also successfully carried out; and hydrogel particles excellent in the quality and performances are efficiently produced. As a means of achieving this object, the process according to the present invention for production of hydrogel particles is a process for production of the hydrogel particles 14 from a high-concentration hydrogel sheet 10 and comprises: a step (a) of cutting a continuous sheet 10 of a crosslinked high-concentration hydrogel polymer of 50 to 80 weight % in solid component concentration every 10 to 100 cm lengthwise of the continuous sheet 10 while running it lengthwise, thereby obtaining cut pieces 12; and a step (b) of continuously supplying the cut pieces 12 (obtained from the step (a)) to a continuous disintegrator 40 to continuously carry out disintegration and discharge under conditions where the supply amount of the cut pieces 12 and the disintegrating and discharging abilities of the continuous disintegrator 40 satisfy (supply amount) </= (disintegrating and discharging abilities), thereby obtaining the hydrogel particles 14.

Description

The method that is used to make the method for hydrogel particle and is used for cutting of high-concentration hydrogel sheet
Technical field
The present invention relates to a kind of method of making the method for hydrogel particle and being used for cutting of high-concentration hydrogel sheet of being used to.Particularly, the present invention relates to: a kind of method that is used to make the graininess hydrogel is included in the process of making the water-absorbing resin grain step that the hydrogel sheet to (manufacturing sheet in advance) water-absorbing resin cuts and pulverizes; And a kind of method that is used for cutting of high-concentration hydrogel sheet, this method is applicable to the above-mentioned method that is used to make the graininess hydrogel.
Background technology
A kind of technology that is used to make hydrogel particle, comprise and make the step that the water-absorbing resin hydrogel sheet is pulverized this hydrogel sheet then, this technology is a kind of known technology that is used to make the water-absorbing resin grain, this water-absorbing resin grain is widely used in for example absorbing material, and this absorbing material is used for for example absorbent products of paper nappy one class.
Proposed a kind of method that is used for making continuously high-concentration hydrogel sheet in the patent documentation 1 hereinafter, comprised the steps: that the aqueous solution of acrylic acid monomer component is fed on the endless belt with for example containing; Then this monomer component is carried out polymerization under the state that leaves static state.A kind of being used for by utilizing a kind of shearing-type primary breaker or cutting and shear mill to pulverize this high-concentration hydrogel sheet to obtain the technology of hydrogel particle wherein also disclosed.Above-mentioned patent documentation discloses and has been suitable for a kind of sieve type pulverizer as pulverizer, and described sieve type pulverizer has a sieve and realizes pulverizing by a fixed blade and shearing between the rotating blade.The hydrogel particle that is produced is carried out drying or pulverizing, to obtain the water-absorbing resin grain.This high-concentration hydrogel sheet is not to form a flat and smooth sheet, but form following a kind of shape, promptly owing to the foaming and intumescing that occurs of boiling in polymerization process and because contraction subsequently causes the thickness of each position to scatter or thickness rises and falls or fluctuates.Above-mentioned patent documentation shows that an advantage of the high-concentration hydrogel sheet of this shape is to be easy to pulverize, thereby is easy to make the water-absorbing resin grain.
Disclose a kind of technology that is used to make fritter shape water-soluble polymer gel in the patent documentation 2 hereinafter, comprised the steps: to utilize a pair of roll-type cutting machine that sheet of water soluble polymer gel is cut into rectangle; Utilize a rotating blade and a fixed blade in the direction that meets at right angle with the roll-type cutting machine they to be cut equally then.Fixed blade is arranged in by under the rectangular sheet of a pair of roll-type cutting machine discharge.Rotating blade axially is arranged on its excircle along a cylindrical revolving body, and utilizes the rotation of this revolving body and rectangular sheet is placed between rotating blade and the fixed blade, thereby cuts this rectangular sheet.Above-mentioned patent documentation shows, even the hard polymer gel also can be easy to form fritter, and adhesion phenomenon also seldom occurs between these fritters.
Disclose a kind of technology that is used to obtain the rectangle gel piece in the patent documentation 3 hereinafter, comprised the steps: to move a continuous aqueous polymer gel sheet; And, in the gap between cutting roller and opposed roller (being arranged in the upside and the downside of serialgram), cut serialgram along its length so that serialgram is opened along horizontal partition by plate-like cutting machine (being arranged on the cutting roller), and longitudinally cut off this serialgram every a clear and definite spacing as follows, promptly be arranged on the same cutting roller and and shred along its axially extended rectangular plate shape rotating blade by one.Wherein also disclose the gel piece that to be generated and for example be ground into granule, thereby obtained the water-absorbing resin grain.Wherein show, even can successfully obtain this gel piece and can not adhere on the cutting blade from the flexible polymer gel film.
[patent documentation 1] JP-A-212204/2002 (Kokai)
[patent documentation 2] JP-A-110510/1986 (Kokai)
[patent documentation 3] European patent specification No.0827443B1
For the prior art that is used to cut hydrogel sheet, can not avoid hydrogel to cling for example cutting tip fully.Because the adhesion and the pinning phenomenon of hydrogel, operation stops, and perhaps must often for example remove the operation of this adhesion material.
Especially, in above-mentioned patent documentation 1 under the disclosed high-concentration hydrogel sheet situation, owing to aforesaid reason, this sheet has the shape that thickness scatters or thickness rises and falls or fluctuates, also because the adhesive force or the adhesivity of this sheet are very strong, so one of them problem is, this sheet certainly will will adhere on the cutting machine, and perhaps cutting cube will certainly bond once more.
In above-mentioned patent documentation 1, high-concentration hydrogel sheet is pulverized by shearing-type primary breaker or cutting and shearing mill.But, if attempt after pulverizing high-concentration hydrogel sheet immediately with this sheet (making continuously) pulverizer of giving without interruption, then will certainly cause adhering to and block the sieve in the pulverizer for example, its reason also is, this high-concentration hydrogel sheet just creates, so be in the condition of high temperature.
For the cutting technique in the above-mentioned patent documentation 2, owing to directly come on the revolving body that is provided with rotating blade by the rectangular sheet of a pair of roll-type cutting machine cutting, the fritter that cuts by rotating blade and fixed blade certainly will glue on the surface of staying revolving body.If this fritter accumulates on the excircle of revolving body, then cutting operation can not carry out become unsatisfactoryly again.
In above-mentioned patent documentation 2, propose, should be cooled to by temperature in about 10～30 ℃ scope in case adhere to gel film.But, in order to allow gel film (may enter state after just having created) under earlier than the prerequisite of supplying, fully cool off to cutting machine near 100 ℃, gel film must be from its process units operation one long segment distance again to cutting machine, perhaps in running, increase by a cooling device, perhaps the speed of service is slowed down so that guarantee cool time.Therefore, the expense of equipment increases, and makes efficient and reduce.
For the cutting technique of above-mentioned patent documentation 3, because serialgram is to cut as follows, promptly, the stroke place in the roll spacing of knife-blade between roller utilize tabular rotating blade that it is shredded in the serialgram, so be difficult to guarantee to cut the whole thickness of serialgram by being entered.Especially, if this high-concentration hydrogel sheet is the form that thickness scatters or thickness rises and falls or fluctuates, then cutting is very difficult.Because serialgram is to move under the state of being clamped (promptly inserting) between cutting roller and the opposed roller, serialgram will certainly cling the surface of cutting roller and opposed roller.Especially, this cutting gel piece causes and certainly will adhere on the opposed roller unsatisfactoryly.
Summary of the invention
One object of the present invention is to realize: the above-mentioned high-concentration hydrogel serialgram that is suitable for making high-performance water-absorbing resin grain is cut effectively, and do not involve for example problem of cutting blade and so on of clinging; And also can successfully carry out crushing operation subsequently; And the splendid hydrogel particle of workmanship and performance effectively.
Technical solution of the present invention is as follows:
The method that is used to make hydrogel particle of the present invention is a kind of method that is used for being made by high-concentration hydrogel sheet hydrogel particle, comprise: step (a), in solid constituent concentration is that the serialgram of the high concentration cross-linked hydrogel polymer of 50～80 weight % is when longitudinally moving, along vertically it being cut of serialgram, thereby obtain cutting cube every 10～100cm; And step (b), with this cutting cube (obtaining) continuous pulverizer of giving without interruption by step (a), and in the supply of cutting cube with pulverize continuously and discharge under the pulverizing of pulverizer and the situation that the discharge ability satisfies this condition of (supply)≤(pulverizing and the discharge ability) continuously, thereby obtain hydrogel particle.
[high-concentration hydrogel sheet]:
Basically, can utilize the known technology of this area to make high concentration cross-linked hydrogel polymer sheet, in conventional art, adopt this and produce the water-absorbing resin grain.In as the disclosed above-mentioned technology of JP-A-212204/2002 (Kokai), practicable a kind of technology is the technology of producing high-concentration hydrogel sheet by the following method, in described method, the water-containing monomer solution that is fed on the endless belt is being left continuous polymerization under the static state.
＜water-containing monomer solution 〉:
At the water-containing monomer solution that is used for producing high-concentration hydrogel sheet, outside the demonomerization component, also comprise other components, for example unsaturated monomer component (for example internal crosslinking agent) and polymerization initiator.
The example of monomer component comprises: anionic unsaturated monomer ((methyl) acrylic acid for example, (anhydrous) maleic acid, itaconic acid, cinnamic acid, vinyl sulfonic acid, propylene toluenesulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, 2-(methyl) third rare acid amides-2-methyl propane sulfonic acid, 2-(methyl) acryloyl ethamine sulfonic acid, 2-(methyl) acryloyl ethamine sulfonic acid, 2-(methyl) acryloyl propyl alcohol sulfonic acid, 2-ethoxy (methyl) acryloyl phosphate) and their salt; The unsaturated monomer that contains mercapto; The unsaturated monomer of phenolic hydroxy group; Amide groups unsaturated monomer (for example (methyl) acrylamide, N-ethyl (methyl) acrylamide, N, N-dimethyl (methyl) acrylamide); And amino unsaturated monomer (for example N, N-dimethylaminoethyl (methyl) acrylate, N, N-dimethyl aminopropyl (methyl) acrylate, N, N-dimethyl aminopropyl (methyl) acrylamide).These monomers can use separately or appropriate combination each other.But, owing to consider following factor: the performance of the water-absorbing resin that is generated; And cost; Hope is with acrylic acid and/or its salt (for example sodium, lithium, potassium, ammonium and amine salt; At first, consider that from the expense angle sodium salt is suitable) as key component.Advantageously, acrylic acid and/or its salt are not less than 70mol% with respect to the consumption of whole monomer component, more advantageously are not less than 80mol%, and more advantageously are not less than 90mol%, particularly advantageously are not less than 95mol%.
For internal crosslinking agent, preferably, the compound that makes each molecule have at least two polymerization unsaturated groups and/or at least two reactive groups carries out combined polymerization or reaction is used as internal crosslinking agent.The object lesson of internal crosslinking agent comprises: N, N '-methylene his dialkylphosphine oxide (methyl) acrylamide, (gathering) ethylene glycol bisthioglycolate (methyl) acrylate, (gathering) third rare propane diols two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, glycerine three (methyl) olefin(e) acid ester, glycerine acrylate methacrylate, ethylene oxide correction trimethyl propane three (methyl) acrylate, pentaerythrite six (methyl) acrylate, triallyl cyanurate, third triallyl isocyanurate, TAP, triallylamine, poly-(methyl) pi-allyl oxyalkanes, (gathering) ethylene glycol bisthioglycolate Synthesis of Oligo Ethylene Glycol, glycerine two glycerin ether that contracts, ethylene glycol, polyethylene glycol, propane diols, glycerine, pentaerythrite, ethylenediamine, carbon ester ethene, propylene carbonate and glycidyl (methyl) acrylate.
Internal crosslinking agent advantageously is 0.005～2mol% with respect to the consumption of monomer component, more advantageously is 0.02～0.5mol%, more advantageously is 0.04～0.2mol%.When the consumption of internal crosslinking agent during less than 0.005mol% or greater than 2mol%, the absorbent properties that obtained may be nonconforming.
Have no particular limits for polymerization initiator.Available example comprises: thermal initiator (for example following persulfate: sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate; Following peroxide: hydrogen peroxide, tert-butyl peroxide, butanone peroxide; And following azo-compound: azo butyronitrile compound, azo amidine compound, ring azo amidine compound, the azo amide compound, alkyl azo-compound, 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two [2-2-imines azo-2-yl] propane) dihydrochloride); And light trigger (for example styrax derivative, benzyl derivative, acetophenone derivs, benzophenone derivates and azo-compound).Consider the factors such as ability of cost and reduction residual monomer content, be fit to use persulfate.In addition, using light trigger and ultraviolet ray also is suitable method.More suitable is to be used in combination light trigger and thermal initiator.
Though not specifically restriction, but the concentration of the monomer component in the water-containing monomer solvent advantageously is not less than 30 weight %, more advantageously be not less than 35 weight %, more advantageously be not less than 40 weight %, more advantageously be not less than 45 weight %, more advantageously be not less than 50 weight %, more advantageously be not less than 55 weight %, more advantageously in the scope of 30～70 weight %, still more advantageously in the scope of 35～60 weight %, yet more advantageously in the scope of 40～60 weight %.When above-mentioned concentration during less than 30 weight %, output is lower.When above-mentioned concentration during greater than 70 weight %, absorbability is relatively poor.
This reaction system for example can add: various blowing agents (for example (hydrogen) carbonate, carbon dioxide, azo-compound, inert organic solvents); Hydrophilic polymer (starch for example, cellulose, starch derivatives, cellulose derivative, polyvinyl alcohol, poly-(acrylic acid) (salt), crosslinked poly-(acrylic acid) (salt)); Various surfactants; Chelating agent; And chain-transferring agent (for example hypophosphorous acid (salt)).In addition, also can add organic powder.
The polymerization of＜continuous static 〉:
Can use the traditional continuous static polymerization technique that is used to make water-absorbing resin grain technology.For instance, can adopt as disclosed technology in the above-mentioned patent documentation 1.
For endless belt and other polyplants, can adopt and the identical technology of traditional continuous static polymerization.Polyplant can be provided with for example heating and cooling mechanism, ultraviolet lamp and decompressor.
Polymerization is carried out under normal pressure usually.But,, also can advantageously when distillating moisture, under the pressure condition that reduces, carry out in order to reduce the boiling point of paradigmatic system.More advantageously, for example, under the normal pressure condition, carry out polymerization for the ease of operation.
Though there is no particular restriction, usually be not less than 50 ℃ for the used temperature of polymerization, advantageously be not less than 60 ℃, more advantageously be not less than 70 ℃, more advantageously be not less than 80 ℃, more advantageously be not less than 90 ℃, more advantageously in 80～105 ℃ of scopes, the most advantageously in 90～100 ℃ of scopes.If temperature is lower than 50 ℃,, not only cause output lower, and the physical property result of water-absorbing resin is also relatively poor because sensitive period and polymerization time prolong.By the way, polymerization time is meant from finishing polymerization initiation conditions (comprise and finish the supply of water-containing monomer solution) to the time that reaches peak temperature.
The polymerization initiation temperature is not less than 50 ℃ usually, advantageously is not less than 60 ℃, more advantageously is not less than 70 ℃, more advantageously be not less than 80 ℃, more advantageously be not less than 90 ℃, more advantageously in 80～105 ℃ of scopes, the most advantageously in 90～100 ℃ of scopes.If the polymerization initiation temperature is lower than 50 ℃,, not only cause output lower, and the physical property result of water-absorbing resin is also relatively poor because sensitive period and polymerization time prolong.If the polymerization initiation temperature is higher than 105 ℃, then nonconforming foaming or expansion may appear.The polymerization initiation temperature can get that muddy, viscosity rises and temperature raises learns from for example water-containing monomer solution becomes.
Though there is no particular restriction, the maximum temperature between polymerization period advantageously is not higher than 150 ℃, more advantageously is not higher than 140 ℃, more advantageously is not higher than 130 ℃, more advantageously is not higher than 120 ℃, still is more advantageously not to be higher than 115 ℃.If above-mentioned maximum temperature is higher than 150 ℃, its shortcoming is that the physical property of polymer that is produced or hydrogel or water-absorbing resin grain can reduce greatly.
Temperature difference T between the maximum temperature between polymerization initiation temperature and polymerization period advantageously is not more than 70 ℃, more advantageously be not more than 60 ℃, more advantageously be not more than 50 ℃, more advantageously be not more than 40 ℃, more advantageously be not more than 30 ℃, the most advantageously be not more than 25 ℃.If Δ T is greater than 70 ℃, its shortcoming is that the physical property of polymer that is produced or hydrogel or water-absorbing resin grain can reduce greatly.
Though there is no particular restriction, polymerization time advantageously is no more than 5 minutes, more advantageously is no more than 3 minutes, more advantageously less than 3 minutes, more advantageously is no more than 2 minutes, yet more advantageously is no more than 1 minute.If polymerization time is during greater than 5 minutes, its shortcoming is that output is lower.
In this polymerization process, after polymerization caused, system temperature raise rapidly, reached for example boiling point of the oligomerization conversion of 10～20mol% afterwards, began polymerization then, discharged water vapour simultaneously to increase the concentration of solid constituent.In polymerization process, cause foam expansion and contraction.Because the water vapor pressure effect between polymerization period causes paradigmatic system to be bubbled, thereby surface area increases.In addition, promote the water vapour volatilization by this, cause contraction then.The hydrogel sheet of this form has good release capability, and for example (it is a kind of polyplant) throws off from the endless belt, and also is ground into particle easily.
The expansion magnifying power of hydrogel sheet between polymerization period advantageously is not less than 2 multiplying powers, more advantageously is not less than 3 multiplying powers, more advantageously is not less than 5 multiplying powers, more advantageously is not less than 10 multiplying powers, yet more advantageously is not less than 20 multiplying powers.Because paradigmatic system is extended between polymerization period, so polymerization begins to carry out when polymerization is extended.
Polymerization obtains high-performance hydrogel or high-performance water-absorbing resin grain by polymerization at high temperature after causing.Polymerization under the normal pressure is favourable polymerization, to such an extent as to having reached, temperature is not less than 100 ℃ in the polymerization conversion process of 40mol%, even and in the polymerization conversion process of 50mol%, still be not less than 100 ℃, more advantageously, to such an extent as to having reached, temperature is not less than 100 ℃ in the polymerization conversion process of 30mol%, even and in the polymerization conversion process of 50mol%, still be not less than 100 ℃, and the most advantageously, to such an extent as to having reached, temperature is not less than 100 ℃ in the polymerization conversion process of 20mol%, even and in the polymerization conversion process of 50mol%, still be not less than 100 ℃.If carry out polymerization under the pressure that reduces equally also is favourable polymerization, to such an extent as to temperature has reached boiling point in the polymerization conversion process of 40mol%, and even still boiling temperature in the polymerization conversion process of 50mol%, more advantageously, to such an extent as to temperature has reached boiling point in the polymerization conversion process of 30mol%, and even still boiling temperature in the polymerization conversion process of 50mol%, and the most advantageously, to such an extent as to temperature has reached boiling point in the polymerization conversion process of 20mol%, and even still boiling temperature in the polymerization conversion process of 50mol%.
Polymerization is carried out on request, water is evaporated simultaneously, thereby the ratio (concentration rate) between the solid constituent concentration of the solid constituent concentration of the formed hydrogel of polymerization and water-containing monomer solution will be advantageously for being not less than in 1.10 the scope, more advantageously be not less than 1.15, more advantageously be not less than 1.20, more advantageously be not less than 1.25.If concentration ratio is less than 1.10, the utilization of polymerization heat can not be said so fully.In this, the solid constituent of water-containing monomer solution is meant monomer and other additives, and does not comprise water or solvent.
For the hydrogel sheet of manufacturing, the concentration of its solid constituent more advantageously in the scope of 52～75 weight %, more advantageously is 55～70 weight % still in the scope of 50～80 weight %.If the solid constituent excessive concentration can see that performance reduces, that is, absorbability reduces and can extract constituent content and increases.If solid constituent concentration is too low, then the load that is applied in the subsequent drying step is heavier.
[serialgram]:
For the serialgram of the high concentration cross-linked hydrogel polymer of making in a manner described, its size is with manufacturing installation and create conditions and change.Usually, the width range of serialgram is 10cm to 3m.The thickness range of serialgram is 1～50mm, but quite disperses with the position is different.In addition, serialgram is not to be flat and smooth sheet, but the form for rising and falling or fluctuating.
By serialgram is longitudinally moved it is supplied with cutting process.Though creating conditions of for example high-concentration hydrogel sheet do not made restriction, the speed of service with serialgram is set in the scope of 2～20m/min usually.
Just after creating by above-mentioned continuous static polymerization, serialgram is under about 60～100 ℃ condition of high temperature usually.But in the present invention, the serialgram under this condition of high temperature can be supplied to cutting step.In addition, also can be not less than 70 ℃ or the serialgram that is not less than under 80 ℃ the condition of high temperature and be supplied to cutting step being in.
[cutting cube]:
Become by the size situation of the made cutting cube of serialgram application target and the desired performance with hydrogel particle, perhaps the performance with high-concentration hydrogel sheet becomes.Especially requirement, the size and dimension of cutting cube is suitable for producing the pulverising step of hydrogel particle.Require this size and dimension to make cutting cube can successfully be supplied to continuous pulverizer by injection mode.
The shape of cutting cube is generally rectangle.But, even be not strict rectangle, but also being fine near the parallelogram or the rhombus of rectangle, this depends on the method for cutting.Outward flange is usually by rectilinear(-al), but if curve also can.
The size of cutting cube long side is determined in the scope of 10～100cm, and the size of its short brink is in the scope of 10～100cm.
In addition, though depend on the situation of employed continuous pulverizer, for example, if the width of serialgram is in the scope of 10～300cm, advantageously be 10～200cm, more advantageously be 10～100cm, but after also can by only along its length but not broad ways cut off serialgram every certain size and obtain cutting cube.
[slit shearing]:
When making cutting cube,, then only obtain the target cutting cube by cutting off serialgram every predetermined interval along its length if the width of serialgram is narrower by serialgram.Usually, vertical cutting spacing of serialgram is to set according to the size of target cutting cube long side.In addition, vertical cutting spacing of serialgram also can be set according to the size of target cutting cube short brink.For example, only longitudinally cut off but not during along transversely cutting, then vertical cutting spacing of serialgram can be set in the scope of 10～100cm preferred 10～50cm every certain size when serialgram.
As a kind of vertical cutting mode, can adopt the cutting mode that serialgram is cut by the engagement between the cutting blade.By engagement cutting is a kind of like this technology, promptly relatively moves with by edge each other the time when cutting blade, and the serialgram that is present in therebetween is cut.
Particularly, can adopt following cutter sweep.
＜fixed blade and rotating blade 〉:
By means of the engagement between a fixed blade and the rotating blade, by serialgram longitudinally being cut off every a determining deviation along the lateral dissection serialgram, wherein, fixed blade is being fixed, and be arranged in along lateral cross on the surface of described serialgram, and wherein, rotating blade on the apparent surface of serialgram, make into the horizontal transverse axis of pivot and along the traffic direction rotation of serialgram.
For fixed blade, can almost with in the one side position contacting of serialgram be provided with the tabular blade of a strip, so that meet at right angle with the traffic direction of serialgram.
Rotating blade can be arranged on the excircle of the single-revolution body that drives by for example motor rotation, thereby blade edge can stretch out along diametric(al).Rotating blade also can be arranged at least two positions on the revolving body circumferencial direction.The cutting spacing of serialgram can be controlled by the rotating speed (being the rotating speed of rotating blade) and the speed of service of serialgram of adjusting revolving body.Usually the rotating speed of rotating blade can be set in the scope that is about 100rpm at the most.When passing through away from serialgram one position with rotating blade in the time of also can making rotating blade cutting serialgram under the both of these case rotating speed of rotating blade different.For example,, can allow the same moved further of operation of rotating blade and serialgram, and after cutting, can allow the rotating blade fast moving, thereby prevent that serialgram or cutting cube from being adhered to, and prepare for next cutting operation when cutting during serialgram.Make the synchronous cutting of translational speed of the translational speed of material to be cut and cutting blade be called the synchronized model cutting, and, for example a kind of low inertia servo motor is used for the motive power of rotating blade.
Can be with the tabular rotating blade of flat rubber belting as rotating blade.The arrangement form at rotating blade edge makes it can be by the form that is meshed with fixed blade by a position, an elongate slot that is had between the edge of this position for itself and fixed blade.Slit between these blade edges can be set in the scope of 0.005～0.05mm, advantageously is 0.01～0.04mm, more advantageously is 0.01～0.03mm.If the slit is too narrow, then owing to for example influence of variations in temperature and so on, blade edge will bump together unfavourably, thereby be worn and damage.If above-mentioned slit is too wide, then be difficult to thin serialgram is cut.
The edge of rotating blade and the edge of fixed blade or layout parallel to each other, or incline towards each other layout.The edge of rotating blade can tilt with the straight flange of fixed blade.In this case, the edge of rotating blade is inevitable to tilt along a cylindrical plane, and the inevitable spirality of blade edge or rotating blade is arranged.In order to reduce to cut resistance, for thin serialgram, be fit to usually set the inclination angle of rotating blade less, and for thick serialgram, be fit to be set greatlyyer.Suitable inclination angle depends on that also serialgram is firmly or soft.Usually, the inclination angle can be set in the scope of about 1～2 degree.
If serialgram is the edge of the edge of the fixed blade that is in tilted layout each other by blade and rotating blade when cutting, then the immediate each other position of engagement, the edge of fixed blade and rotating blade moves to the other end by an end of serialgram width gradually, thereby forms the joint-cutting of serialgram transverse width direction.The cutting effectively thereby serialgram is smoothed.Because each cutting position constantly is basically on the some position in a place, is pressed on the serialgram for a long time so can prevent the surface of fixed blade and rotating blade, thereby is adhered to unfavourably.
The material of fixed blade and rotating blade can adopt habitual blade material.For instance, comprise carbon steel, Sweden's steel, bearing steel, pottery, spring steel, powder metallurgical technique (PIM) high-speed steel, mould steel, alloy tool steel, superalloy, high-speed steel, stellite, stainless steel and ferrotitanium (ferrotic) steel.When requiring decay resistance, be fit to adopt the martensite type stainless steel (SUS440C for example, SUS420J2).
＜rotating blade and rotating blade 〉:
Above-mentioned rotating blade can be arranged on the surface and the back side of serialgram Face to face, thereby serialgram be cut by the engagement between these rotating blades.
In addition, in this case, the rotating blade on two faces of serialgram may or be parallel to each other layout, or is in tilted layout mutually.The inclination angle of the rotating blade on two faces can be different.The material of rotating blade and configuration state can be set according to the situation of the above-mentioned engagement between fixed blade and the rotating blade.
＜prevent to adhere to:
For the member (for example cutting blade) that constitutes cutting machine, possible situation is: in order to make serialgram can not adhere to basically, these members are made of fluorine resin material, only carry out on the surface of member for preventing to adhere to the measurement of being carried out (for example measurement scribbles fluororesin).For the surface treatment mode that is used to prevent to adhere to, can adopt resin (for example fluororesin) coating and other modes, for example carbonization, nitrogenize, heavy chromium is handled, and atom (atomlly) is handled, resinoid bond (redux) is handled, teflon (tef-lock), spray tungsten, hard chromium is electroplated and sprayed ceramic.
Also can on the surface of cutting tip, be formed for preventing the male and fomale(M﹠F) and/or the groove that adhere to.
For the structure of cutting machine, in order to prevent to adhere to, more preferably, except cutting necessary member (for example fixed blade and rotating blade), the scope inner structure member that passes through at serialgram and cutting cube should lack as much as possible.For instance, more preferably, the edge of open cutting position, rather than lid is set around cutting position.
[transversely cutting]:
When the width of serialgram during greater than the size of target cutting cube, effective is that broad ways is cut off serialgram at regular intervals.
Transverse cuts can be set in the scope of 10～100cm at interval.
The transversely cutting serialgram can carry out before or after slit shearing.Usually, after transversely cutting becomes certain width, easier carrying out by carry out this operation that slit shearing obtains cutting cube every a determining deviation.
For the mode of transversely cutting serialgram, can adopt various sheet cutting modes.Preferred serialgram adheres to few method.
For example, can utilize a rotating blade on serialgram, longitudinally make continuous otch mode and with serialgram by the spacing transversely cutting that limits, described rotating blade is along rotating in the plane of the traffic direction of serialgram.This cutting mode is called as vertical cutter (slitter) mode.For the cutting method of this vertical cutter mode, known have following three kinds of modes: scrape and cut (razor cut), shearing and indentation and cut (score cut).Variety of way all can adopt.With regard to cutting power, shearing and score cuts are outstanding.Suitable manner has winding (wrap) longitudinal joint to scrape to cut, twine longitudinal joint to shear and twine the longitudinal joint indentation to cut, in these cutting modes, serialgram be wrapped in as to be cut serialgram passed through through line (pass line) accept be cut around roller or the bottom knife.
In indentation butt formula, the plate-like rotating blade is crushed on along on the serialgram of the end face operation of accepting roller, thereby in the mode of crush-cutting the serialgram that is clipped in rotating blade and accept between the roller is cut.Can pressure be applied to structural elements by for example air pressure, for example on the bolster of plate-like rotating blade.Air pressure can be set in the scope of 0.3～1.0Mpa, advantageously is 0.4～0.8MPa, more advantageously is 0.4～0.6MPa.With regard to improving durability, make that advantageously the surfacing of accepting roller is harder than the material of rotating knife sheet.
In cut mode, the side that serialgram is provided to the plate-like rotating blade is forced through the position with a side of another rotating blade part of joining, thereby serialgram is cut by shear action.Apply in 5～15% the scope that gap between the blade of shear action can be set at material thickness to be cut.When cutting blade was one-sided edge blade, it can be by being used with mode that the pairing blade section contacts gently.In addition, can also apply contact pressure by a disc spring or air pressure.
In addition, also can adopt by above-mentioned various cutting modes are made up or improve the cutting mode that is arranged to.
In addition, for the transversely cutting mode, similar with above-mentioned slit shearing mode, can take measures on cutting blade surface and/or component surface (for example fluororesin-coated) is in case adhere to, described member and cutting blade are adjacent, and may be subjected to the adhesion of serialgram.
[the anti-medium that adheres to]:
Prevent that the effective way that serialgram adheres to from being, cut fixed blade and the rotating blade and the close cutting position of serialgram and may provide the anti-medium that adheres to serialgram position contacting place (for example being used to provide the member of fixed blade and rotating blade) to being used to.The anti-medium that adheres to is effectively for preventing that serialgram from adhering on the member (for example cutting blade), in addition, also is effective for the adhesion once more between the cutting section of the serialgram after preventing to cut.
Available anti-adhesion medium can be can not change the serialgram quality, reduce its performance or for the step of back, for example pulverising step plays any dysgenic liquid or gas.Concrete example comprises water, warm water and water vapour.Available warm water is about 60～90 ℃ warm water.
The anti-medium that adheres to can be supplied to the precalculated position by the injection apparatus of for example sprayer and shower nozzle one class.With regard to rotating blade,, also be effective and just be fed to the position that the rotating blade rotation passes through even the anti-medium that adheres to is not fed to cutting position.
The anti-supply that adheres to medium is according to the structure of for example cutting mode and cutting blade and different.
For instance, when water during, be the serialgram of 2～15m/min (rice/minute) for the speed of service as antiseized attached medium, output can be able to be set at about 5～2000g/min (Grams Per Minute).In addition, for warm water, also can adopt supply in the same scope.For water vapour, consider that supply can be set in the scope of about 25～10000g/min owing to spread the quantity that the factor of a class is scattered and disappeared.
[prevention thermal deformation]:
Having a kind of may be that distortion appears in the possible heat that produce because following dissection of cutter sweep (comprising cutting blade, for example rotating blade and fixed blade) that is used to cut serialgram.If this thermal deformation, then for example the position of cutting blade, size and dimension can change a little, and the gap between the cutting blade also can change, thus their acutance variation, and perhaps cutting blade is worn easily or damages.
Thereby cutter sweep can be provided with the device that is used to prevent or prevent thermal deformation.For this solar heat protection anamorphic attachment for cinemascope, can adopt with habitual cutting machine on the thermal deformation that is provided with prevent structure and anti-locking apparatus identical mechanism of thermal deformation and device.
The anti-above-mentioned supply that adheres to medium also can be used as the anti-locking apparatus of thermal deformation.Also can exercise to prevent this function of thermal deformation from cutting blade elimination heat by spray the anti-mode that adheres to medium or allow anti-adhesion medium contact to cutting blade with cutting blade.
For the medium that is used to prevent thermal deformation, preferred thermal conductivity height or the big medium of thermal capacity.And preferred properties does not reduce the medium of cutting blade acutance.
Water, warm water or water vapour can be used for preventing adhering to, and also can be used for preventing thermal deformation, are quite outstanding handling on this point easily simultaneously.The supply of water, warm water or water vapour can be set in as in the relevant aforementioned range that prevents to adhere in the identical text.But, in above-mentioned supply scope, set a bigger supply not only for the purpose that prevents to adhere to, and prevent that for abundant execution the function of thermal deformation from all being effective.
[situation of serialgram in the cutting process]:
Serialgram can effectively prevent by state or the traffic direction of serialgram in cutting process in adhesion on the cutting machine and the bonding between the cutting cube.
When longitudinally cutting off at a certain distance, serialgram can vertically move by the mode that suspends from top to bottom.The fixed blade of cutting machine and rotating blade or rotating blade are arranged on two surfaces of serialgram of vertical operation Face to face.If serialgram is cut, then the cutting cube of separating from serialgram is owing to deadweight descends, and the composition member (for example cutting blade) that therefore can not adhere to cutting machine is gone up but is separated immediately.Adhesion once more between the cut length also can be avoided.Because serialgram falls because of deadweight, so, also the phenomenon that serialgram adheres to transfer roller or conveyer can not take place even do not use transfer roller or conveyer operation serialgram.If the cutting cube that falls owing to conducting oneself with dignity is received by the inlet (being set in the descent path below) of continuous pulverizer, then they can securely and effectively be supplied to continuous pulverizer.
When allowing serialgram, rather than when allowing serialgram move fully straight down, also can longitudinally serialgram be cut off along the operation of downward-sloping direction.While, the vertical component that acts on the gravity on serialgram or the cutting cube was separated cutting cube smoothly from serialgram in this case.In addition,, can prevent that also serialgram is pressed on the conveyer forcefully, therefore seldom adhere to thereon even the conveyer that for example is in tilted layout is used for making the serialgram slant operation.
[pulverizing of cutting cube]:
The cutting cube that downcuts from serialgram is continuously supplied to a continuous pulverizer, so that pulverize continuously, and satisfy under the situation of (supply)≤(pulverizing and the discharge ability) in the supply of cutting cube and the pulverizing and the discharge ability of continuous pulverizer, pulverize and discharge, thereby obtain hydrogel particle.
What can be used as continuous pulverizer is the device that is suitable for continued operation between the various pulverizers that are used for traditional water-absorbing resin manufacturing technology.
For example, can use the screw press type pulverizer.The structure of this screw press type disintegrator is: a screw rod rotates in a cylindrical barrel, and the cutting cube that has been fed to the material inlet of this cylinder is fed forward, pulverized when stirring by the screw rod rotation simultaneously, then, the pulverizing piece is extruded by a perforation extruding plate at the front end place that is arranged in this cylinder, thereby obtains the suitable hydrogel particle in aperture of particle diameter and perforation extruding plate.The aperture is big more, and the particle diameter that generates hydrogel particle is just big more.But have a kind of tendency to be: the aperture of perforation extruding plate is not to conform to the particle diameter of the hydrogel particle that is generated, but the particle diameter of the hydrogel particle that is obtained is less than the aperture.In addition, also can rotating blade be set and cut pending material in perforation extruding plate inside.With regard to concrete structure, can adopt appropriate combination structure with the structure that known screw press type pulverizer was identical already.As the object lesson of screw press type pulverizer, can use the device of buying on the market, for example cutmixer (making) and Dome Gran (making) by Fuji Paudal Co., Ltd by Hiraga Kosakusho.In addition, also can adopt the single-screw extruder that only has a screw rod, and double helix or four screw extruders.When screw rod when being a plurality of, the direction of rotation of screw element can be identical, also can be different.
For the screw press type pulverizer, the pulverization process quantity of hydrogel particle or withdrawal rate can change by the rotating speed of adjusting screw rod in the unit interval.
Can be used as continuous pulverizer equally has: tower mill, for example Rote Plex (being made by Hosokawa Mikron Co., Ltd); Spiral pulverizer, for example special-purpose triple helical formula Alpha (Triple-Special-Screw Type Alpha) (making) by Nippon SpindleProduction; And the continuous rotational shear device of double helical form, for example GainLx (registration mark) crushing machine (making) by Horai Co., Ltd.
For continuous pulverizer, if cutting cube is in large supply when its pulverizing and discharge ability, then cutting cube will be stagnated in device unfavourably, and perhaps cutting cube is unfavourably with its internal blocking.If cutting cube in this device by excessive agitation or rub, just then the performance of hydrogel can be changed or reduce.
Therefore, pulverize and discharge is in the supply of cutting cube and carries out continuously under the pulverizing of pulverizer and the condition that the discharge ability satisfies (supply)≤(pulverizing and the discharge ability) continuously.
The cylinder of pulverizer can be provided with a thermoregulation mechanism continuously, is used to cool off or heat pending material.
[hydrogel particle]:
The hydrogel particle of discharging from continuous pulverizer is for example to be the graininess shape of spherical.The shape of hydrogel particle is according to the pulverizing situation and different.Except sphere, also can have other shapes, for example ellipsoid and elongated cylinder.Irregularly shaped in addition in addition.Even the polymerization in the manufacture process comprises foaming process, most of generation particle also all is the uncertain shape that does not contain any bubble, and reason may be that the bubble size that produces in the above-mentioned foaming process is bigger.
The particle diameter of hydrogel particle can be set in the scope of 0.5～3mm.
Hydrogel particle can be used for various use occasions because of the characteristics that itself had.They can be used for for example hygienic article, agricultural and gardening.They can mix to guarantee the flowability of particle with fine particulate inorganic thing (for example bentonite, zeolite, silica).
Handle by drying, hydrogel particle can be used as dry state water-absorbing resin grain.What be suitable as seasoning is the drying means that makes that material well contacts with hot-air and/or heat-transfer area when mobile, for example stirs seasoning, fluidized-bed layer seasoning and pneumatic conveying drying method.
In addition, the also available for example various treat liquid of hydrogel particle are handled, and perhaps carry out drying after handling.In addition, also can carry out surface treatment, for example surface-crosslinked processing.
The invention effect is as follows:
In the technology that is used for making hydrogel particle of the present invention, the higher hydrogel particle (obtaining the splendid water-absorbing resin grain of water absorbing properties thus) of quality and performance can effectively make by the technology that comprises the steps: when serialgram vertically moves, longitudinally cut off the serialgram of high concentration cross-linked hydrogel polymer every a determining deviation, thereby obtain cutting cube; Then, satisfy under the situation of this condition of (supply)≤(pulverizing and the discharge ability) in the supply of cutting cube and the pulverizing and the discharge ability of continuous pulverizer, with the cutting cube continuous pulverizer of giving without interruption that generates, pulverizing continuously and discharge, thus the acquisition hydrogel particle.
To not be supplied under the situation of continuous pulverizer because of forming the remaining hydrogel serialgram of cutting cube, and then must make the supply of serialgram just in time conform to the pulverizing and the discharge ability of continuous pulverizer.If the supply of serialgram is too big, then pulverizer can be blocked by too much serialgram continuously.If the supply of serialgram is too little, just then continuously pulverizer can on serialgram, apply bigger pressure, thereby unfavourably with its interruption, to such an extent as to without interruption become impossible.
Because the supply (being manufacture) of serialgram depends on create conditions (for example polymerization procedure), so the pulverizing and the discharge ability of pulverizer must reach the level consistent with the supply of serialgram continuously.But, this means that the selection of continuous pulverizer or design difficulty increase, thereby make the cost of equipment increase.At this moment the situation that is occurred is, if the change of creating conditions of serialgram then also must be changed continuous pulverizer.
Therefore in the present invention, after serialgram obtains cutting cube, under the condition of (supply)≤(pulverizing and the discharge ability), pulverize continuously and discharge is effective.
As a kind of method that is used for the slit shearing serialgram, if when vertically moving serialgram, by the engagement slit shearing serialgram between fixed blade and the rotating blade (wherein, fixed blade is fixed and lateral cross is arranged on the surface of serialgram, and rotating blade is on the apparent surface of serialgram, make a horizontal transverse axis for pivot, and the traffic direction rotation along serialgram), then serialgram can be cut effectively, and high-concentration hydrogel sheet (having strong viscosity) can adhere on cutting blade or other bulking blocks aptly, and this sheet blocking device aptly.
By specific descriptions hereinafter, will know above and other objects of the present invention and advantage more.
Description of drawings
Fig. 1 is that the integral body of manufacturing installation constitutes view, shows to be used to implement a kind of pattern of the present invention.
Fig. 2 is from the front elevation shown in the face side of serialgram.
Fig. 3 is a perspective view (a) and a front elevation (b), shows the blade portion structure of cutting machine.
Fig. 4 is a profile, shows another pattern that is used to cut.
Fig. 5 shows the detailed structure view of slitter.
Fig. 6 is that the integral body of cutting operation part constitutes view, shows to be used to implement another kind of pattern of the present invention.
Description of reference numerals
10: the high-concentration hydrogel serialgram
12: cutting cube
14: hydrogel particle
20: slitter
22: accept roller
23: groove
24: the plate-like rotating blade
26,38: nozzle
30: cutting machine
32: the sheet fixed blade
34: revolving body
36: the sheet rotating blade
40: continuous pulverizer
42: inlet
46: screw portion
48: the perforation extruding plate
C: the position of engagement
X: gap
The specific embodiment
Below the present invention is described in detail.But, scope of the present invention is not limited to these descriptions.And in the scope that does not deviate from spirit of the present invention, also can implement other embodiments except that following example by the suitable improved procedure of example hereinafter.
[unitary construction]:
In the pattern of implementing as illustrated in fig. 1 and 2 of the present invention, hydrogel particle is made by high-concentration hydrogel sheet.
Hydrogel sheet 10 is to manufacture banded serialgram by the continuous static polymerization on the endless belt, and longitudinally moves continuously by the conveying device of for example conveyer.This serialgram is shown the flat piece shape in the drawings, but in fact, its thickness is fluctuation or fluctuating shape, and perhaps thickness changes, and perhaps width also changes.
The hydrogel serialgram 10 of along continuous straight runs operation is supplied on the slitter 20.The speed of service that is fed to the serialgram 10 on the slitter is 4.5m/min, and the width of this serialgram 10 is about 80cm.
＜slitter 〉:
Slitter 20 is provided with: one is arranged in and accepts roller (receivingroll) 22 on serialgram 10 back sides; With one be arranged in serialgram 10 lip-deep plate-like rotating blades 24.As shown in Figure 2, plate-like rotating blade 24 is separated by a distance laterally arranges two at least along serialgram 10.Plate-like rotating blade 24 incision serialgrams 10 to be forming vertically joint-cutting continuously on serialgram 10, thus with it along transversely cutting.The position of formed joint-cutting can be according to different change of layout quantity and spacing of plate-like rotating blade 24 with quantity on the serialgram 10.
Fig. 5 shows the detailed structure embodiment of slitter 20; Fig. 5 (a) is the structure in the edge incision serialgram 10 of plate-like rotating blade 24 in the rip cutting mode, described rotating blade is made by the corrosion resisting stainless steel that scribbles fluororesin, the blade edge diameter is 7.5cm, is configured to almost and is made by the corrosion resisting stainless steel that scribbles fluororesin equally and diameter is that the surface of accepting roller 22 of the cylinder form of a 14cm contacts.Push plate-like rotating blade 24 these modes by for example applying the pressure of air pressure and so on, serialgram 10 is cut from upside.
Structure among Fig. 5 (b) is as follows: same as above, make by the corrosion resisting stainless steel that scribbles fluororesin, diameter is that the roller 22 of accepting of 14cm is provided with a groove 23, and the open circumferential of this groove 23 is a blade section.Make and the blade edge diameter is that the side of rotating blade 24 of the one-sided limit of the plate-like form of a blade of 7.5cm is arranged to almost the contacted form of a medial surface with groove 23 by the corrosion resisting stainless steel that scribbles fluororesin.In cut mode, serialgram 10 is cut by shear action under the state between the open circumferential of side that places plate-like rotating blade 24 and groove 23.
As shown in Figure 1, be used to spray nozzle 26 as the water of anti-adhesive liquor body be arranged in plate-like rotating blade 24 near.By water is ejected into plate-like rotating blade 24 from nozzle 26, the material adhesion that is prevented serialgram 10 to plate-like rotating blade 24, thereby kept the acutance of plate-like rotating blade 24.
For for the serialgram 10 of slitter 20 transversely cuttings, its traffic direction is become along the direction straight down of accepting roller 22 by horizontal direction.
＜cutting machine 〉:
Serialgram 10 along the operation of direction decline straight down is supplied on the cutting machine 30.
Be shown specifically as Fig. 3 (a), cutting machine 30 has a straight flange fixed blade 32, and this blade crosses the width of serialgram 10 and is bearing on the surface of serialgram 10.In addition, cutting machine 30 also has: single-revolution body 34 be arranged in the position in the face of fixed blade 32, and the width that crosses serialgram 10 is arranged on the back side of serialgram 10, and is rotating along the traffic direction of serialgram 10 and to advance; And a sheet rotating blade 36, stretch out by the neighboring of revolving body 34 along diametric(al), and along the neighboring of revolving body 34 and revolving body 34 axially a little obliquely spirality arrange.Because sheet rotating blade 36 is to be arranged in such a way on the neighboring of revolving body 34, thus this rotating blade can be on the back side of serialgram 10, make axle (not shown) (crossing the width of serialgram 10) and rotate along the traffic direction of serialgram 10 for center of rotation.
Fixed blade 32 is made by the corrosion resisting stainless steel that scribbles fluororesin, and its blade edge width is 7cm.Revolving body 34 is made by the corrosion resisting stainless steel that scribbles fluororesin, and its external diameter is 20cm.Sheet rotating blade 36 is made by the corrosion resisting stainless steel that scribbles fluororesin, and it is 7cm from the outstanding length in the neighboring of revolving body 34.
By revolving body 34 rotations, the edge of the edge of fixed blade 32 and sheet rotating blade 36 passes through each other in intermeshing mode.Because sheet rotating blade 36 spirality tilt, so the position of engagement C between sheet rotating blade 36 and the fixed blade 32 moves to other end side along axis direction by an end side surface gradually.By moving of this position of engagement C, serialgram 10 is able to be cut open at position of engagement C place.Serialgram 10 only contacts with the periphery of sheet rotating blade 36 at position of engagement C with fixed blade 32, and does not contact with for example neighboring of revolving body 34, thereby can not adhere on it.
By the way, shown in Fig. 3 (b), between the edge of the edge of fixed blade 32 and sheet rotating blade 36, have an elongated interval, i.e. gap x.By this gap of suitable adjustment x, can make that acutance is good, perhaps can improve the durability of fixed blade 32 and sheet rotating blade 36.
Vertical cutting spacing of serialgram 10 can become according to the relation between the speed of service of the revolution that spacing or quantity and revolving body 34 are set of the sheet rotating blade 36 on the revolving body 34 and serialgram 10.
As shown in Figure 1, be used to spray the nozzle 38 (same as above) of preventing the adhesive liquor body and be configured to tilt, and tilt, thereby prevent that serialgram 10 from adhering on fixed blade 32 and the sheet rotating blade 36 at revolving body 34 at fixed blade 32.The nozzle of setting in that revolving body 34 tilts 38 is injected into the outside of water from sheet rotating blade 36 rotation movings range on the sheet rotating blade 36.
As shown in Figure 2, the serialgram 10 that is separated by slitter 20 broad ways also is cut machine 30 and longitudinally cuts off every a determining deviation.Thereby obtained approximate rectangular cutting cube 12.In Fig. 2, shown in cutting cube 12 be entirely rectangle.But because rectangle warpage a little, the shape that is cut the cutting cube 12 that the inclination sheet rotating blade 36 of machine 30 cuts out also can be approximately parallelogram or rhombus.
As shown in Figure 1, if the serialgram 10 of Yi Donging is cut machine 30 and longitudinally cuts off straight down, the cutting cube 12 that is then generated is owing to deadweight falls.
＜continuous pulverizer 〉:
As shown in Figure 1, the continuous pulverizer 40 of screw press type is arranged on cutting machine 30 belows.
Has an inlet 42 that is used to inject pending material at the continuous top of pulverizer 40.The shape and size of inlet 42 make the cutting cube of being supplied by cutting machine 30 12 to inject by landing safely.For example, this inlet is the rectangular aperture of 50cm * 50cm size.
Below inlet 42, be provided with: a cylindrical barrel part 44; And the screw portion 46 of a rotation in this cylindrical portions may 44.Screw portion 46 is driven by for example motor rotation.Be provided with some apertures at cylindrical portions may 44 front ends and run through wherein perforation extruding plate 48.
The cutting cube 12 that is fed to inlet 42 moves forward, and the rotation by screw portion 46 simultaneously and stir cylindrical portions may 44 in and pulverize is extruded from perforation extruding plate 48 at last, thereby forms hydrogel particle 14 and from continuous pulverizer 40 discharges.The particle diameter of the hydrogel particle 14 that is generated obviously less than the perforation extruding plate 48 the aperture.For example, be that the particle diameter that 16 perforation extruding plate 48 is extruded the hydrogel particle 14 that obtains is about 2.5mm from the aperture.
[improving the embodiment of cutting machine]:
Fig. 4 shows the structure that is different from the cutting machine 30 of implementing above-mentioned pattern of the present invention.
Revolving body 34 and sheet rotating blade 36 are arranged in the surface and the back side of the serialgram 10 that moves straight down.Be used to spray the nozzle 38 of preventing the adhesive liquor body and also be arranged on two surfaces.
Since about two rotary bodies 34 all rotate along the traffic direction of serialgram 10, so their certainty be rotated along opposite directions.
For be arranged on one of left rotation and right rotation body 34 go up, for the sheet rotating blade 36 of the axioversion of these rotary bodies, left and right sides sheet rotating blade 36 passes through mutually with the position of the serialgram 10 of intermeshing mode between.Serialgram 10 is cut by the mode that an end side surface of serialgram 10 moves to other end side by the position of engagement C between the left and right sides sheet rotating blade 36.
In this Implementation Modes of the present invention, because two blades of cutting serialgram 10 are sheet rotating blade 36, the translational speed between them is very big, so serialgram 10 can be cut fast and forcefully.
In this embodiment of the present invention, similar equally with the of the present invention above-mentioned embodiment shown in Fig. 3 (b), between the edge of a pair of sheet rotating blade that is engaged with each other 36,36, have a gap x.Especially, because two sheet rotating blades 36,36 are mobile for rotation, so suitably adjusting play x is extremely important.
[another embodiment of the present invention]:
Embodiments of the present invention as shown in Figure 6 and above-mentioned embodiment of the present invention are different on the arrangement of slitter 20 and cutting machine 30.
Serialgram 10 results that vertically cut by means of passing slitter 20 are not operation straight down, but are tilted to down operation.Conveyer 50 is arranged on the downstream of slitter 20, and the feed surface of conveyer 50 tilts downwards.The feed surface of conveyer 50 is handled by for example fluororesin technology, thereby reduces the degree of adhesion of itself and serialgram 10.
Cutting machine 30 is on the downstream of conveyer 50, be obliquely installed below it.Serialgram 10 is longitudinally cut off by cutting machine 30, cutting cube 12 free-fallings that generated then.As a result, initial because their downward-sloping moving of the effect of inertia of operation, to such an extent as to up to since the gravity effect from the fixed blade 32 of cutting machine 30 and sheet rotating blade 36 separately till, and after this because gravity effect and landing straight down.Therefore, the inlet 42 of continuous pulverizer 40 need be arranged according to the descent path of cutting cube 12.
The specific descriptions of preferred implementation
Hereinafter, by the following preferred implementation the present invention is done more specifically to describe.But, in any case the present invention all be not limited thereto.
The evaluation result that is used to implement concrete technology of the present invention and performance thereof is described as follows:
[being used to measure the method for performance]:
＜absorbability (GV) 〉:
Measure unloaded absorbability.Evenly place nonwoven bag (in the 60mm * 60mm), to immerse the moisture sodium chloride solution (physiological saline) of 0.9 weight % then in the sample of 0.2g.After 30 minutes, sack is pulled, use whizzer then with 250 * 9.81m/s 2Speed (250G) was dewatered 3 minutes, measured the weight W 1 (g) of sack afterwards.In addition, do not having to carry out above-mentioned identical process under the situation of water-absorbing resin, and measuring the weight W 0 (g) of product.Afterwards, calculate unloaded absorbability according to following formula by these weight W 1 and W0:
GV (the g/g)=weight (g) of sample [(W1-W0) /]-1
The constituent content of＜water extractable 〉:
Moisture NaCl solution (physiological saline) example of the 0.9 weight % of 184.3g is gone in the plastic containers with cover that capacity is 250ml to weigh.Then, the sample of 1.00g is added in this aqueous solution, stirred 16 hours, from resin, extract, to measure the quantity that to extract component thereby can extract component.
＜salt flow conductivity SFC 〉:
Its measuring method is carried out according to salt flow conductivity (SFC) test of JPA-509591/1997 (kohyo).
[embodiment 1]:
＜manufacturing hydrogel sheet 〉:
The following solution of predetermined amount of flow is mixed together with preparation monomer liquid.
48.5 weight % aqueous naoh solution 73.5g/s
53.9 weight % water-containing acrylic acid solution 169.2g/s
By dissolving 77.4 parts heavy 50 weight % water-containing acrylic acid solution, 2-hydroxyl first-2-aminomethyl phenyl ethyl ketone of 0.781 part heavy, 0.849 part heavy 46 weight % moisture penta sodium diethylenetriamine penta acetum and the polyethyleneglycol diacrylate (mean molecule quantity: 523) be dissolved in the solution 1.43g/s for preparing together of 21.0 parts of weights.
The temperature of the monomer liquid that is generated is stable in the time of about 95 ℃.
Monomer liquid is without interruption to supply line, and in this supply pipeline, constantly stir, then the flow of the moisture sodium peroxydisulfate solution of 3 weight % with 3.40g/s imported in this monomer liquid, thereby form mixing material.The monomer concentration of this mixed liquor is 45 weight %, and degree of neutralization is 70mol%.
Device as the belt polymerization is as lower device: being provided with an effective length is that 7.0m, width are the endless belt that 1.5m and surface scribble fluororesin; And a UV lamp is arranged at belt top; And with bottom and periphery in about 100 ℃ time heating and adiabatic; And, be provided with an air intake duct to reclaim the moisture content of evaporation at central portion.
Above-mentioned mixed liquor is fed on the belt polyplant, is 5.6mm until the thickness of monomer, thereby carries out polymerization continuously with the belt speed of 4.5m/min.Resulting is that solid constituent content is that 60 weight %, the wide 80cm of being about of the rear panel that contracts, the thick 2～20mm of sheet (it is because produce wrinkle after expanding in the process of shrinking that this dispersing appears in thickness, and is to cause because these wrinkles may drop on the top of each other) and surface temperature are about 70 ℃ banded aquogel polymer sheet.
＜manufacturing cutting cube 〉:
Immediately the banded hydrogel serialgram that is produced is supplied to slitter by conveyer belt.The basic structure of this slitter is shown in Fig. 5 (a).With diameter is that 75mm, thickness are that the score cutter type rotating blade of 2mm is arranged in three places at interval, and with respect to these rotating blades the roller of accepting that one diameter is 140mm is set.When serialgram was placed the score cutter place, its broad ways was divided into four under the air pressure of 0.40MPa.
By the oss-divided serialgram of slitter because deadweight and change the state that traffic direction becomes vertically to hang down and be supplied to a cutting machine with accepting roller.
The basic structure of this cutting machine is as follows as shown in Figure 3: a fixed blade, thickness are 20mm, to the length of its blade edge be 70mm; One roll forming revolving body, diameter are 200mm; And a spiral sheet rotating blade, be arranged at the neighboring of revolving body, thickness is 14mm, to the length of its blade edge be 70mm, width is 1.4m.The sheet rotating blade only is provided with in a position of revolving body.Gap between fixed blade and the rotating blade is adjusted into about 0.01mm.This cutting machine is half synchronized model rotary cutter.
Revolving body cuts every 15cm serialgram with the revolution of 30rpm along the vertically continuous of serialgram.Resulting is the rectangle cutting cube that is almost 20cm * 15cm.
According to observations, serialgram does not stick to the score cutter blade of slitter or accepts on the roller, perhaps adheres on fixed blade, rotating blade or the revolving body of cutting machine.Between the cutting section of cutting cube, also can't see adhesion once more.But, when operation has been carried out for a long time, can see a little that serialgram for example adheres on the cutting blade, and see between the cutting section of cutting cube and adhering to once more.But when reality is used and have no problem.
＜pulverize continuously:
With the aperture of extruded hole is that the cutmixer of 16mm will be pulverized by the cutting cube that cutting machine is made, thereby obtains hydrogel particle.
As cutmixer is 72 type cutmixers (being made by Hiraga Kosakusho: the disposal ability when the screw rod revolution is 105rpm=about 6t/ hour).This device is the continuous pulverizer of screw press type.The inlet of cutmixer is about 50cm * 50cm, and can receive the cutting cube that is produced by abovementioned steps really.
The screw rod revolution is set in 15rpm, and it is 0.86t/ hour that cutmixer is pulverized the disposal ability of discharging then to hydrogel particle.The supply that is supplied to the cutting cube of cutmixer by cutting machine is 0.66t/ hour.This satisfies the condition of (being supplied to the supply of cutmixer)≤(pulverizing and the discharge ability).
The engagement of cutmixer is good, thereby can not occur silting up, and the discharge state is good equally, thereby makes discharge carry out continuously.Also can't see at the loading hopper that injects part and to silt phenomenon up.
＜manufacturing water absorbing resin particle 〉:
The hydrogel particle that to discharge from cutmixer with 180 ℃ hot blasts was pulverized it with kibbler roll, thereby is obtained particulate water-absorbing resin grain (1) to obtain dry material in dry 40 minutes afterwards.From water-absorbing resin grain (1), sieve the interior particle of 300～600 μ m particle size range with sieve, measure the physical property of screening particle then.Absorbability is 42 (g/g), and the constituent content that available water is extracted is 14 weight %.Subsequently, heat-treat with butanediol/propylene glycol/water/24% NaOH system with mortar mixer at 212 ℃.The physical property of the water-absorbing resin grain after the processing: absorbability is 30 (g/g), and salt flow conductivity (SFC) is 40.Confirmed already that the water-absorbing resin grain of manufacturing in fact fully had the performance of water-absorbing resin grain.
[embodiment 2]:
The manufacturing of＜cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, described serialgram is by the technology manufacturing identical with embodiment 1.
Employed slitter is the score cutter identical with embodiment 1, but its score cutter blade and accept roller and all scribble fluororesin.With the mode of embodiment 1, serialgram laterally is divided into four parts with the width of 20cm.
The serialgram that will vertically hang down from the slitter is supplied to cutting machine.
The structure of cutting machine is basically with embodiment 1, but its fixed blade and accept roller coat fluororesin is arranged.At the revolving body revolution is under the situation of 30rpm, and serialgram is cut along the vertically continuous of serialgram every 15cm.Acquisition is almost the rectangle cutting cube of 20cm * 15cm.According to observations, serialgram does not adhere on slitter or the cutting machine.Between the cutting section of cutting cube, also can't see adhesion once more.So after operation was carried out for a long time, the above-mentioned adhesion and the situation that adheres to once more were all very slight.
＜pulverize continuously:
Pulverize cutting cube with cutmixer, thereby obtain hydrogel particle with embodiment 1.
＜manufacturing water absorbing resin particle 〉:
With hydrogel particle being handled, thereby obtain particulate water-absorbing resin grain (2) with embodiment 1 the same technology.With the mode of embodiment 1, the screening particle size range is the particle of 300～600 μ m from water-absorbing resin grain (2), and measure the physical property of screening particle then: absorbability is 42 (g/g), and the constituent content that available water is extracted is 14 weight %.Subsequently, carry out heat treatment with embodiment 1.The physical property of the generation material after the heat treatment: absorbability is 30 (g/g), and SFC is 40.
Obtain the same water-absorbing resin grain of physical property and embodiment 1.
[embodiment 3]:
＜manufacturing cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, fast serialgram by the technology manufacturing identical with embodiment 1.
Employed slitter is the score cutter the same with embodiment 1, but its rotating blade and accept roller and all scribble fluororesin.Use nozzle to spray water to rotating blade.The scope of watering amount is 5～10cc/ minute.
With the mode of embodiment 1, serialgram laterally is divided into four parts every the width of 20cm.
The serialgram that will vertically hang down from the slitter is supplied to cutting machine.
The structure of cutting machine is basically with embodiment 1, but its fixed blade and rotating blade scribble fluororesin.In fixed blade and the rotating blade each is equipped with a nozzle and sprays water to it, and is provided with a device to this nozzle water supply.The scope of watering amount is 5～10cc/ minute.Revolving body cuts every 15cm serialgram with the revolution of 30rpm along the vertically continuous of serialgram.Resulting is the rectangle cutting cube that is almost 20cm * 15cm.
According to now examining, serialgram does not adhere on slitter or the cutting machine.Between the cutting section of cutting cube, also can't see adhesion once more.After operation is carried out for a long time in addition, can't see above-mentioned adhesion, also can't see adhesion once more.
＜pulverize continuously:
Under the treatment conditions identical, use with the cutmixer of embodiment 1 and pulverize cutting cube, thereby obtain hydrogel particle with embodiment 1.
＜manufacturing water absorbing resin particle 〉:
With the PROCESS FOR TREATMENT hydrogel particle of embodiment 1, thereby obtain particulate water-absorbing resin grain (3).With the mode of embodiment 1, the particle of screening particle size range 300～600 μ m from water-absorbing resin grain (3), measure the physical property of sieving particle then: absorbability is 42 (g/g), the constituent content that available water is extracted is 14 weight %.Subsequently, carry out the heat treatment identical as embodiment 1.The physical property of the generation material after the heat treatment: absorbability is 30 (g/g), and SFC is 40.Obtain the same water-absorbing resin grain of physical property and embodiment 1.
[embodiment 4]:
The manufacturing of＜cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, described serialgram is by the technology manufacturing identical with embodiment 1.
Employed slitter laterally is divided into four parts with serialgram every the width of 20cm whereby with the score cutter of embodiment 1.
The serialgram that will vertically hang down from the slitter is supplied to cutting machine.
The basic structure of cutting machine as shown in Figure 3.Diameter is the revolving body of 200mm, and thickness is 14mm, be that 70mm, width are that the spirality rotating blade of 1.4m is arranged apart in the left and right sides to the length of its blade edge.On each revolving body, be provided with a plurality of rotating blades.Gap between the rotating blade is adjusted into about 0.01mm.This cutting machine is complete synchronized model rotary cutter.The revolution of revolving body is decided to be 30rpm, and serialgram is every 15cm vertically cutting continuously along serialgram.Resulting is the rectangle cutting cube that is almost 20cm * 5cm.According to observations, gel film does not for example adhere on rotating blade or the revolving body, and does not see that adhesion is once more arranged between cutting section yet.After operation is carried out for a long time, some above-mentioned adhesions or adhesion once more appear a little in addition.But when using, reality has no problem.
＜pulverize continuously:
Under treatment conditions, use with the cutmixer of embodiment 1 cutting cube is pulverized, thereby obtain hydrogel particle with embodiment 1.
＜manufacturing water-absorbing resin grain 〉:
With the PROCESS FOR TREATMENT hydrogel particle of embodiment 1, thereby obtain particulate water-absorbing resin grain (4).With the mode of embodiment 1, the screening particle size range is the particle diameter of 300～600 μ m from water-absorbing resin grain (4), measures the physical property of screening particle then.Absorbability is 42 (g/g), and the constituent content that available water is extracted is 14 weight %.Subsequently, carry out the heat treatment identical as embodiment 1.The physical property of heat treated generation material: absorbability is 30 (g/g), and SFC is 40.Obtain the same water-absorbing resin grain of physical property and embodiment 1.
[embodiment 5]:
The manufacturing of＜cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, described serialgram is by the technology manufacturing identical with embodiment 1.
Employed slitter is the score cutter device that scribble fluororesin identical with embodiment 2, whereby with serialgram every the width of 20cm along laterally being divided into four parts.
The serialgram that will vertically hang down from the slitter is supplied to cutting machine.
Cutting machine is a structure with the same complete synchronized model rotary cutter that scribbles fluororesin of embodiment 4.Revolving body cuts every 15cm serialgram with the revolution of 30rpm along the vertically continuous of serialgram.Resulting is the rectangle cutting cube that is almost 20cm * 15cm.According to now examining, gel film does not for example adhere on rotating blade or the revolving body, and does not see that adhesion is once more arranged between cutting section yet.In addition the operation carry out for a long time after, above-mentioned adhesion and once more the adhesion all very slight.
＜pulverize continuously:
Under treatment conditions, use with the cutmixer of embodiment 1 cutting cube is pulverized, thereby obtain hydrogel particle with embodiment 1.
＜manufacturing water absorbing resin particle 〉:
With the PROCESS FOR TREATMENT hydrogel particle identical, thereby obtain particulate water-absorbing resin grain (5) with embodiment 1.With the mode of embodiment 1, the screening particle size range is the particle of 300～600 μ m from water-absorbing resin grain (5), measures the physical property of screening particle then.Absorbability is 42 (g/g), and the constituent content that available water is extracted is 14 weight %.Subsequently, carry out the heat treatment identical as embodiment 1.The physical property of heat treated generation material: absorbability is 30 (g/g), and SFC is 40.Obtain the same water-absorbing resin grain of physical property and embodiment 1.
[embodiment 6]:
The manufacturing of＜cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, described serialgram is by the technology manufacturing identical with embodiment 1.
The structure of this slitter is basic shown in Fig. 5 (b), is as follows: the cutting machine cutter, and it is 75mm and the plate-like rotating blade that scribbles fluororesin for diameter; Scribble the cutting machine bottom knife of fluororesin, its diameter is 150mm, has slitter shaft (roller of accepting with groove); And the device of on these shear-blades, sprinkling water (sprinkling amount: 5～10cc/ minute).When last bottom knife contacts each other gently, and when this contact pressure remained unchanged, serialgram laterally was divided into four parts every the width edge of 20cm.
The serialgram that will vertically hang down from the slitter is supplied to cutting machine.
Cutting machine is a structure with the same complete synchronized model rotary cutter that scribbles fluororesin of embodiment 4.It also is provided with following structure: the nozzle of water spray, and the device that supplies water.The scope of watering amount is 5～10cc/ minute.
Revolving body cuts every 15cm serialgram with the revolution of 30rpm along the vertically continuous of serialgram.Resulting is the rectangle cutting cube that is almost 20cm * 15cm.According to observations, gel film does not for example adhere on rotating blade or the revolving body, and does not see that adhesion is once more arranged between cutting section yet.Operation also is like this after having carried out for a long time.
＜pulverize continuously:
Under treatment conditions, use with the cutmixer of embodiment 1 cutting cube is pulverized, thereby obtain hydrogel particle with embodiment 1.
＜manufacturing water absorbing resin particle 〉:
With the PROCESS FOR TREATMENT hydrogel particle identical, thereby obtain particulate water-absorbing resin grain (6) with embodiment 1.With the mode of embodiment 1, the screening particle size range is the particle of 300～600 μ m from water-absorbing resin grain (6), measures the physical property of screening particle then.Absorbability is 42 (g/g), and the constituent content that available water is extracted is 14 weight %.Subsequently, carry out the heat treatment identical as embodiment 1.The physical property of heat treated generation material: absorbability is 30 (g/g), and SFC is 40.Obtain the same water-absorbing resin grain of physical property and embodiment 1.
[comparing embodiment 1]:
The manufacturing of＜cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, described serialgram is by the technology manufacturing identical with embodiment 1.
Employed slitter is for the score cutter device that scribble fluororesin identical with embodiment 2, with the mode of embodiment 1, whereby with serialgram every 20 width along laterally being divided into four parts.
(width: about 20cm) the SGE-220-model sheet granulator by 22cm cuts into effective cutting width (being made by Horai Co., Ltd) to a slice in four that serialgram was divided into.This sheet granulator is a kind of device that sheet material is cut; specifically: carry out the rip cutting cutting by vertical cutting blade of forming by a roll-type cutting machine; and be arranged on the revolving body and by a fixed blade and and carry out transverse cuts along its axially extended straight flange sheet rotating blade; wherein, the bottom of the contiguous above-mentioned vertical cutting blade of these fixed blades and rotating blade is provided with.The revolution of transverse cuts rotating blade is set at 250rpm, and the spacing between rotating blade and the fixed blade is arranged in the scope of about 0.05～0.08mm.In order to prevent to adhere to, spray water at the vertical and horizontal cutting part with the sprinkling amount of 40～50cc/min.
But the problem of appearance is: a part of serialgram adheres to the rotating blade that for example is used for transverse cuts; Perhaps occur between the cutting section of cutting cube adhering to once more; Perhaps rotating blade and divide around the guard section of rotating blade neighboring between the gap be cut piece and block.Even adhesion material is removed also start-up operation again, also can occur immediately blocking.Therefore, serialgram can not cut continuously.
＜pulverize and the manufacturing water absorbing resin particle:
(size: about 5mm * 60mm) uses the cutmixer identical with embodiment 1 to pulverize to the spherical water-setting blob of viscose of being made up of acquired continuous sheet before ending in operation, then by the technology manufacturing water-absorbing resin grain identical with embodiment 1.For the particle that particle size range in the generation water-absorbing resin grain (7) is 300～600 μ m, its absorbability is 40 (g/g), and the constituent content of available water extract is 18 weight %.Subsequently, carry out the heat treatment identical as embodiment 1.The physical property of heat treated generation material: absorbability is 29 (g/g), and SFC is 20.Like this, proved already, and, then can produce the inappropriate substandard products of water absorbing properties if cutting operation can not successfully carry out.
[embodiment 7]:
Except the following change of creating conditions, the manufacturing of cutting cube and pulverizing continuously, and the manufacture of water-absorbing resin grain is with embodiment 1.
For the cutmixer identical with embodiment 1, the screw rod revolution is set at 75rpm.Therefore, be supplied to 0.66t/ hour supply of cutmixer with respect to cutting cube, the pulverizing of cutmixer and discharge disposal ability are 4.29t/ hour.This satisfies the condition of (supply)≤(pulverizing and the discharge ability) fully.Obtain the target hydrogel particle, and cutting cube can not silt, even can not stagnate in the inlet place of cutmixer temporarily up.
For the water-absorbing resin grain (8) in 300～600 μ m, its absorbability is 43 (g/g) for the particle size range that has obtained by the processing mode the same with embodiment 1, and the constituent content of available water extract is 12 weight %.Subsequently, carry out heat treatment as embodiment 1.The physical property of heat treated generation material: absorbability is 31 (g/g), and SFC is 43.Obtain the water absorbing properties water-absorbing resin grain high than embodiment 1.
[comparing embodiment 2]:
Except the following change of creating conditions, the manufacturing of cutting cube and pulverizing continuously, and the manufacture of water-absorbing resin grain is with embodiment 1.
For the cutmixer the same with embodiment 1, the screw rod revolution is set at 5rpm.Therefore, be supplied to 0.66t/ hour supply of cutmixer with respect to cutting cube, the pulverizing of cutmixer and discharge disposal ability are 4.29t/ hour.Wherein, supply)＞(pulverizing and the discharge ability), the condition of satisfied (supply)≤(pulverizing and the discharge ability).Therefore, compare with the supply of serialgram, this pulverizing and withdrawal rate are too little.Thereby the engagement in the cutmixer is relatively poor, silts up in the state at inlet place to such an extent as to cause cutting cube.In the cutmixer to silt the time up also oversize, thereby obtain under the state that hydrogel particle just stirs in cutmixer.
For the water-absorption particle (9) in the particle size range that has obtained by the processing mode identical with embodiment 1, absorbability is 41 (g/g), and the constituent content of available water extract is 17 weight %.Subsequently, carry out the same heat treatment with embodiment 1.Absorbability is 29 (g/g) in the physical property of the heat treatment material of manufacturing, and SFC is 30.Water absorbing properties is poorer than embodiment's 1.
[comparing embodiment 3]:
Except the following change of creating conditions, the manufacturing of cutting cube and pulverizing continuously, and the manufacture of water-absorbing resin grain is with embodiment 1.
With the wide 80cm of being about of sheet and sheet thick be the serialgram cutmixer of giving with embodiment 1 without interruption of 2～20mm, serialgram is remained on the state that the edge is not cut, by slitter or cutting machine.The screw rod revolution is set at 50rpm.
Because it is too fast that pulverizing and discharge velocity are compared with the supply rate of serialgram, so the serialgram of Zhu Ruing is torn inadequately continuously, so that uncontrollablely tear re-injecting of sheet material.Therefore, continued operation becomes impossible.
[embodiment 8]:
Basic adopt device and the step identical, but some device construction and step change with embodiment 1.Below the main different piece of describing.
The manufacturing of＜cutting cube 〉:
Utilize conveyer belt to be supplied to slitter by the serialgram that hydrogel sheet is formed, described serialgram is not established any slitter by the technology manufacturing identical with embodiment 1.Then, the serialgram that will be in the state that vertically hangs down is supplied to a cutting machine.The structure of cutting machine is identical with embodiment 1 basically.In fixed blade and the rotating blade each is equipped with a nozzle and sprays water to it, and is provided with a device to this nozzle water supply.The watering amount is about 1300cc/min.The revolution of rotating blade is set at 30rpm, and every vertically continuous the cut serialgram of 15cm along serialgram.What the result obtained is the rectangle cutting cube of about 80cm * 15cm.
According to observations, serialgram does not adhere on the cutting machine.Even after operation has been carried out for a long time, also can't see adhesion at all.The cutting acutance of rotating blade and fixed blade does not reduce in time yet.
＜pulverize continuously:
Utilization is pulverized by the cutting cube that obtains in the abovementioned steps with the cutmixer of embodiment 1.The screw rod revolution is set at 85rpm.The supply that is supplied to the cutting cube of cutmixer by cutting machine is 0.66t/ hour.This supply is to be supplied to the supply 0.66t/hr of hydrogel sheet of cutting step and the summation of the output 0.08t/hr that sprays in cutting step.Utilize cutmixer that hydrogel particle is pulverized and the disposal ability of discharge is 4.86/hr.This satisfies the condition of (supply)≤(pulverizing and the discharge ability) fully.Processing can successfully be carried out, and cutting cube is not the inlet place of silting or even stagnate in temporarily cutmixer up.Thereby obtain the hydrogel particle of target smoothly.
＜manufacturing water-absorbing resin grain 〉:
With the mode of embodiment 1, the hydrogel particle that had obtained from abovementioned steps is already handled, thereby obtained water-absorbing resin grain (10).For one group of particle diameter in the particle size range in the water-absorbing resin grain (10) that is generated is 300～600 μ m, absorbability is 43 (g/g), and the constituent content of available water extract is 12 weight %, and SFC is 43.The water absorbing properties of these water-absorbing resin grains more outstanding than among the embodiment 1.
Under the prerequisite that does not break away from spirit of the present invention or its scope, can change various details of the present invention.In addition, the purpose of description of the preferred embodiment of the invention that the front provided not is in order to limit by claim and to be equal to the defined the present invention of part only in explanation.

Claims (9)

1. method that is used to make water absorbing resin particle comprises:
Polymerization water-containing monomer solution is the high concentration cross-linked hydrogel polymer sheet of 50～80 weight % to obtain solid constituent concentration, described water-containing monomer solution comprises acrylic acid and/or its salt key component as monomer component, and comprises the internal crosslinking agent of 0.005～2mol%;
Step (a) when the serialgram of high concentration cross-linked hydrogel polymer longitudinally moves, along vertically every 10～100cm it being cut of described serialgram, thereby obtains cutting water-setting blob of viscose; And
Step (b), described cutting water-setting blob of viscose is continuously supplied to a continuous pulverizer, so that satisfy under the situation of this condition of (supply)≤(pulverizing and the discharge ability) in the supply of cutting water-setting blob of viscose and the pulverizing and the discharge ability of continuous pulverizer, pulverize continuously and discharge, thereby obtain hydrogel particle;
Dry described hydrogel particle is to obtain described water absorbing resin particle.
2. the method that is used to make water absorbing resin particle according to claim 1, it is characterized in that, in step (a), described serialgram is longitudinally cut off by the engagement between a fixed blade and the rotating blade, wherein, described fixed blade is being fixed, and be arranged in a face side of described serialgram along lateral cross, and wherein, described rotating blade apparent surface's side of described serialgram, make into pivot along the axle of lateral cross and along the traffic direction rotation of described serialgram.
3. the method that is used to make water absorbing resin particle according to claim 1, it is characterized in that, step (a) comprising: step (a-1) by one along the rotating blade that rotates in the plane of the traffic direction of described serialgram, becomes described serialgram the width of 10～100cm along transversely cutting; And step (a-2), the described serialgram along transversely cutting is longitudinally cut off, be the cutting cube of 10～100cm thereby the acquisition width dimensions is 10～100cm, length dimension.
4. the method that is used to make water absorbing resin particle according to claim 3 is characterized in that, in step (a-1), described cutting is carried out in the score cuts mode.
5. the method that is used to make water absorbing resin particle according to claim 1 is characterized in that, step (b) adopts a screw press type pulverizer as described continuous pulverizer.
6. the method that is used to make water absorbing resin particle according to claim 1, it is characterized in that, step (a) uses one to have the cutting machine of a member as cutting machine, described member comprises that one is used to cut the cutting blade of described serialgram, wherein, described member adheres to prevent the water gel through handling.
7. the method that is used to make water absorbing resin particle according to claim 1, it is characterized in that step (a) comprises step (a-3), step (a-3) is for offering a medium one cutter sweep that is used to cut described serialgram, wherein, described medium is water or water vapour.
8. according to each described method that is used to make water absorbing resin particle among the claim 1-7, it is characterized in that the water absorbing resin particle that is obtained is surface-crosslinked.
9. the method that is used to make water absorbing resin particle according to claim 7 is characterized in that described medium is a warm water.
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